JPH0454934B2 - - Google Patents
Info
- Publication number
- JPH0454934B2 JPH0454934B2 JP9152582A JP9152582A JPH0454934B2 JP H0454934 B2 JPH0454934 B2 JP H0454934B2 JP 9152582 A JP9152582 A JP 9152582A JP 9152582 A JP9152582 A JP 9152582A JP H0454934 B2 JPH0454934 B2 JP H0454934B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- present
- emulsion
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 silver halide Chemical class 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 35
- 229910052709 silver Inorganic materials 0.000 claims description 31
- 239000004332 silver Substances 0.000 claims description 31
- 150000001875 compounds Chemical group 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 description 25
- 239000010410 layer Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 108010010803 Gelatin Proteins 0.000 description 12
- 229920000159 gelatin Polymers 0.000 description 12
- 239000008273 gelatin Substances 0.000 description 12
- 235000019322 gelatine Nutrition 0.000 description 12
- 235000011852 gelatine desserts Nutrition 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 12
- 206010070834 Sensitisation Diseases 0.000 description 11
- 230000008313 sensitization Effects 0.000 description 11
- 238000011161 development Methods 0.000 description 9
- 230000018109 developmental process Effects 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 239000011241 protective layer Substances 0.000 description 8
- 230000001235 sensitizing effect Effects 0.000 description 7
- 150000003568 thioethers Chemical class 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XPAZGLFMMUODDK-UHFFFAOYSA-N 6-nitro-1h-benzimidazole Chemical compound [O-][N+](=O)C1=CC=C2N=CNC2=C1 XPAZGLFMMUODDK-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- IFVYHJRLWCUVBB-UHFFFAOYSA-N allyl thiocyanate Chemical compound C=CCSC#N IFVYHJRLWCUVBB-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical group C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- JXUKLFVKZQETHF-UHFFFAOYSA-N 1-$l^{1}-selanyl-n,n'-dimethylmethanimidamide Chemical compound CNC([Se])=NC JXUKLFVKZQETHF-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 description 1
- YBMTWYWCLVMFFD-UHFFFAOYSA-N 3-methylbutyl 3,4,5-trihydroxybenzoate Chemical compound CC(C)CCOC(=O)C1=CC(O)=C(O)C(O)=C1 YBMTWYWCLVMFFD-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- BQCIJWPKDPZNHD-UHFFFAOYSA-N 5-bromo-2h-benzotriazole Chemical compound C1=C(Br)C=CC2=NNN=C21 BQCIJWPKDPZNHD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical class N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 239000000555 dodecyl gallate Substances 0.000 description 1
- 235000010386 dodecyl gallate Nutrition 0.000 description 1
- 229940080643 dodecyl gallate Drugs 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JGEMYUOFGVHXKV-OWOJBTEDSA-N fumaraldehyde Chemical compound O=C\C=C\C=O JGEMYUOFGVHXKV-OWOJBTEDSA-N 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QJQRNDGUWQVAEV-AAFSJPGBSA-M sodium bisulfite adduct Chemical compound [Na+].[O-]S(=O)(=O)C([C@H]1N(C(C2=C3)=O)C=C(C1)/C=C/C(=O)N(C)C)NC2=CC1=C3OCO1 QJQRNDGUWQVAEV-AAFSJPGBSA-M 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 1
- FZHLWVUAICIIPW-UHFFFAOYSA-M sodium gallate Chemical compound [Na+].OC1=CC(C([O-])=O)=CC(O)=C1O FZHLWVUAICIIPW-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
Description
本発明はハロゲン化銀写真感光材料に関し、更
に詳しくは、感度およびカブリが改良されたハロ
ゲン化銀写真感光材料に関する。
写真画像の質を低下させないで感度を増大する
ことは写真感光材料使用者の根強いしかも継続的
な要請である。これに対して写真業界では種々の
研究の結果、いくつかの増感技術が開発されてき
た。その中に効果が大きく実用性の高い技術とし
てチオエーテル化合物をハロゲン化銀乳剤の製造
時に於て、増感剤として用いることが知られてい
る。例えば米国特許第2521926号、同3021215号、
同3038805号、同3506443号、同3057724号、同
3062646号、同3574709号、同3622329号、同
3625697号明細書等には、乳剤製造の化学熟成時
又は塗布直前にチオエーテル化合物を存在せしめ
ることにより、乳剤の写真感度を上昇せしめる技
術が提示されている。
しかし、これらチオエーテルに非常に効果的な
増感性をもつものの、写真感光材料としての製品
に用いてゆくには未だに技術的に未解決の多くの
問題を残している。その中でも致命的な大きな問
題としてチオエーテルの添加効果の不安定性があ
げられる。即ちチオエーテルを含有する塗布乳剤
の乾燥条件の変化、その乳剤中の添加剤の変化、
また、できあがつた感光材料の現像処理方法等の
条件の変化で著しいカブリの増大が起ることがあ
り、増感効果の目的は達せられたとしてもカブリ
の増加からその製品としての価値は減少する。逆
にカブリが発生しなくとも上記のような諸条件の
変化でその増感作用が全く消滅することもある。
カブリをおさえるために化学熟成をひかえたり、
あるいはカブリ防止剤を加えるなどの処置がとら
れるがこのことにより増感性は著しくそこなわれ
チオエーテルを用いる意味が無くなつてしまう。
また現像処理条件によつて低かぶり濃度、高感度
を保証しようとすると新製品開発毎に最適の処理
条件を開発、指定することとなり使用者にとつて
も製造者にとつても必ずしもメリツトは大きくな
い。
本発明の第1の目的はカブリの上昇を伴なうこ
となく、感度を安定に著しく高めたハロゲン化銀
写真感光材料を提供することにある。
本発明の第2の目的は経時による感度の低下の
改善されたハロゲン化銀写真感光材料を提供する
ことにある。
本発明の第3の目的は最高濃度及びコントラス
トを高めたハロゲン化銀写真感光材料を提供する
ことにある。
本発明者等は上記の目的に対して広範な探索研
究の結果、下記一般式()で表わされる化合物
の少なくとも1種を含有することを特徴とするハ
ロゲン化銀写真感光材料によつて達せられること
を見出した。
一般式()
式中、R1,R3,R4及びR6は炭素数1〜5まで
の低級アルキル基を表し、R2,R5は炭素数1〜
15までのアルキル基、アリール基、アラルキル
基、ヒドロキシアルキル基またはヘテロ環基を表
す。
A,A′及びBはアルキレン基、アリーレン基、
アラルキレン基又はフルオロアルキレン基を表
し、これは同じであつても異なつていてもてもよ
い。)
上記のR1,R3,R4及びR6において炭素数1〜
5の低級アルキル基としては例えばメチル、エチ
ル、プロピル、ブチル、ペンチル基などが挙げら
れる。R2,R5の炭素数1〜15までのアルキル基
としては、例えばCH3,C11H23,C15H31あるい
はCCl3基などで、アリール基としては例えばフ
エニル基、p−クロロフエニル基などが挙げられ
る。アラルキル基としては例えばベンジル基、フ
エネチル基、
The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material with improved sensitivity and fog. Increasing the sensitivity without reducing the quality of photographic images is a persistent and continuing desire of users of photographic materials. In response to this, several sensitization techniques have been developed in the photographic industry as a result of various studies. Among these, it is known that a thioether compound is used as a sensitizer in the production of silver halide emulsions as a highly effective and highly practical technique. For example, US Patent No. 2521926, US Patent No. 3021215,
Same No. 3038805, No. 3506443, No. 3057724, Same No.
No. 3062646, No. 3574709, No. 3622329, No.
No. 3,625,697 and other publications propose a technique for increasing the photographic sensitivity of an emulsion by making a thioether compound present during chemical ripening during emulsion production or immediately before coating. However, although these thioethers have very effective sensitizing properties, there are still many unresolved technical problems in their use in products as photographic materials. Among these, a major and fatal problem is the instability of the effect of adding thioether. That is, changes in the drying conditions of a coated emulsion containing a thioether, changes in additives in the emulsion,
In addition, changes in conditions such as the development method of the finished photosensitive material may cause a significant increase in fog, and even if the purpose of the sensitizing effect is achieved, the increased fog reduces the value of the product. Decrease. Conversely, even if no fogging occurs, the sensitizing effect may disappear completely due to changes in the conditions described above.
In order to suppress fog, we refrain from chemical aging,
Alternatively, measures such as adding an antifoggant are taken, but this significantly impairs the sensitization, and the use of thioether becomes meaningless.
Furthermore, if you try to guarantee low fog density and high sensitivity through development processing conditions, you will have to develop and specify the optimal processing conditions for each new product development, which is not necessarily a great benefit for both users and manufacturers. do not have. A first object of the present invention is to provide a silver halide photographic material that stably and significantly increases sensitivity without increasing fog. A second object of the present invention is to provide a silver halide photographic material with improved sensitivity deterioration over time. A third object of the present invention is to provide a silver halide photographic material with increased maximum density and contrast. As a result of extensive exploration research, the present inventors have achieved the above object by creating a silver halide photographic light-sensitive material characterized by containing at least one compound represented by the following general formula (). I discovered that. General formula () In the formula, R 1 , R 3 , R 4 and R 6 represent lower alkyl groups having 1 to 5 carbon atoms, and R 2 and R 5 represent lower alkyl groups having 1 to 5 carbon atoms.
Represents up to 15 alkyl, aryl, aralkyl, hydroxyalkyl or heterocyclic groups. A, A' and B are alkylene groups, arylene groups,
It represents an aralkylene group or a fluoroalkylene group, which may be the same or different. ) The number of carbon atoms in R 1 , R 3 , R 4 and R 6 above is 1 or more
Examples of the lower alkyl group of 5 include methyl, ethyl, propyl, butyl, and pentyl groups. Examples of the alkyl group having 1 to 15 carbon atoms in R 2 and R 5 include CH 3 , C 11 H 23 , C 15 H 31 or CCl 3 group, and examples of the aryl group include phenyl group and p-chlorophenyl group. Examples include. Examples of aralkyl groups include benzyl group, phenethyl group,
【式】など、ヒドロキシアルキ ル基としては例えばヒドロキシエチル基、[Formula] etc., hydroxyalkyl Examples of the group include hydroxyethyl group,
【式】基、[Formula] group,
【式】 基、【formula】 basis,
【式】基などを挙げること
ができる。ヘテロ環基としては例えばピロリル
基、ピペリジル基などを挙げることができる。
A,A′及びBにおけるアルキレン基としては
例えばエチレン基、プロピレン基、ブチレン基或
は
基などでアリレン基としては例えばフエニレン基
が挙げられる。
又アラルキレン基としては、例えば[Formula] Groups, etc. can be mentioned. Examples of the heterocyclic group include a pyrrolyl group and a piperidyl group. Examples of alkylene groups in A, A' and B include ethylene group, propylene group, butylene group, or Examples of the arylene group include a phenylene group. Further, as the aralkylene group, for example,
【式】基、[Formula] group,
【式】基などが挙
げられる。
フルオロアルキレン基としては、例えば−CF2
CF2−基が挙げられる。
以下に本発明に関る前記化合物の具体例を挙げ
るが、無論本発明はこれらの使用に限定されるも
のではない。
本発明に関る前記化合物は、乳剤層、該乳剤層
に隣接するその他の層(例えば保護層)に、或は
そのいづれにも含有させることができる。添加量
は本発明のハロゲン化銀写真感光材料に用いられ
たハロゲン化銀1モル当たり10mgから1gが好ま
しく、さらに好ましくは20mg〜300mgがよい。添
加時期は前記ハロゲン化銀乳剤の塗布時または塗
布前の任意の時期でよいが、含有させる層が乳剤
層の場合は化学熟成以降、塗布の間に添加するの
が好ましい。
本発明に係るハロゲン化銀乳剤層には各種のハ
ロゲン化銀を使用することができる。たとえば塩
化銀、臭化銀、塩臭化銀、沃臭化銀あるいは塩沃
臭化銀などである。ハロゲン化銀粒子の結晶形、
結晶構造、粒径、粒径分布等には限定はない。た
とえば結晶形は立方体でも八面体でも14面体でも
よいし正常晶でも双晶であつてもよい。また粒子
分布の広い乳剤でもよいし、単分散乳剤でもよ
い。
結晶構造は一様なものでも、内部と外部が異質
の組成であつてもよいし、層状構造をなしていて
も、またエピタキシヤル接合によつて組成の異な
るハロゲン化銀が接合されていてもよい。また潜
像を主として表面に形成するものでも内部に形成
するものでもよい。
前記ハロゲン化銀乳剤は、通常行なわれる化学
増感即ち、硫黄増感法としてチオ硫酸ソーダ、ア
リルチオカルバミド、チオ尿素、アリルチオシア
ネートなどを用いて増感でき、貴金属増感法とし
ては、塩化白金酸カリウム、塩化パラジウム酸ア
ンモニウム或いはルテニウム、ロジウム、イリジ
ウム、プラチニウムなどの貴金属塩も使用でき
る。又これら貴金属塩と硫黄増感剤との併用、さ
らには助剤的にロダンアンモンとの組合せによつ
ても増感することができる。
さらにセレン増感法として例えばセレノウレ
ア、N−Nジメチルセレノウレア、N−ジメチル
セレノウレアなどを用いた方法、還元増感法とし
ては錫塩を用いる方法、ポリアミン類による方
法、第四級アンモニウム塩を用いた方法によつて
も増感することができる。
また、ポリアルキレンオキサイド化合物による
増感法、チオエーテル類による増感法も用いるこ
とができる。
本発明に関るハロゲン化銀乳剤は増感色素を用
いて所望の感光波長域に感色性を付与することが
できる。増感色素としては、種々のものを用いる
こともでき、それぞれ増感色素を1種あるいは2
種以上組合せて用いることができる。
本発明に有利に用いられる色素類としては、シ
アニン、ヘミシアニン、ロダシアニン、メロシア
ニン、オキソノール、ヘミオキソノールなどのメ
チン色素およびスチリール色素などがあげられ
る。
特に米国特許第2213995号、同第2503776号、同
第2945763号、独国特許第929080号、同第2049967
号各明細書、特公昭43−13821号、同44−32753
号、同46−18106号、同47−8741号、同47−37443
号各公報、特開昭48−89722号公報に記載の増感
色素類が本発明において有効である。
その主なる具体的色素としては3,3′−ジ−
(3−スルホプロピル)セレナカルボシアニンヒ
ドロキシド、5,5′−ジフエニル−3,3′−ジ−
(3−スルホプロピル)オキサシアニンヒドロキ
シド、5,5′−ジフエニル−3,3′−ジ−(3−
スルホプロピル)オキサカルボシアニンヒドロキ
シド、3−アリル−5−〔1−メチル−2(1H)
ピペリジリデン〕ローダニン、3−(4−スルホ
ブチル)−1′−エチル−5′−メチルセレナ−2′−シ
アニンヒドロキシド、1−ヒドロキシエチル−3
−フエニル−5−〔3(3−スルホプロピル)−2
−ベンゾオキサゾリニデン〕エチリデン−2−チ
オヒダントインナトリウム塩、5,5′−ジクロロ
−9−エチル−3,3′−ジ−(3−スルホプロピ
ル)オキサカルボシアニンヒドロキシド、5,
5′−ジフエニル−9−エチル−3,3′−ジ(3−
スルホプロピル)オキサカルボシアニンヒドロキ
シド、5,5′,6,6′−テトラクロロ−1,1′−
ジエチル−3,3′−ジ−(4−スルホブチル)ベ
ンゾイミダゾロカルボシアニンヒドロキシドナト
リウム塩、5,5′−ジ−(ブトキシカルボニル)−
1,1′−ジエチル−3,3′−ジ−(3−スルホプ
ロピル)ベンゾイミダゾロカルボシアニンヒドロ
キシド、5,5′−ジクロロ−1,3′−ジエチル−
6′−メチル−3−(4−スルホブチル)ベンゾイ
ミダゾロオキサカルボシアニンヒドロキシド、
5,5′−ジクロロ−9−エチル−3,3′−(ジカ
ルボキシエチル)−チアカルボシアニンヒドロキ
シド、5,5′−ジクロロ−3,9−ジエチル−
3′−(3−スルホプロピル)−チアカルボシアニン
ヒドロキシド、5,5′−ジメチル−9−エチル−
3,3′−ジ−(3−スルホプロピル)チアカルジ
(3−スルホプロピル)4,5,4′,5′−ジベン
ゾチアカルボシアニンヒドロキシド、9−エチル
−3,3′−ジ(3−スルホプロピル)−5,6,
5′,6′−ジベンゾオキサカルボシアニンヒドロキ
シドなどをあげることができる。
本発明に係るハロゲン化銀乳剤は安定剤、カブ
リ抑制剤として例えば米国特許第2444607号、同
第2716062号、同第3512982号、同第3342596号各
明細書、独国特許第1189380号、同第2058626号、
同第211841号各明細書、特公昭43−4133号、同39
−2825号各公報、特開昭50−22626号、同50−
25218号各公報などに記載の方法を適用してよく、
特に好ましい化合物としては、4−ヒドロキシ−
6−メチル−1,3,3a,7−テトラザインデ
ン、4−ヒドロキシ−シクロペンタノ〔f〕−1,
3,3a,7−テトラザインデン或は没食子酸エ
ステル(例えば没食子酸イソアミル、没食子酸ド
デシル、没食子酸プロピル、没食子酸ナトリウ
ム)、メルカブタン類(1−フエニル−5−メル
カブトテトラゾール、2−メルカブトベンゾチア
ゾール)ベンゾトリアゾール類(5−ブロムベン
ゾトリアゾール、4−メチルベンゾトリアゾー
ル)、ベンゾイミダゾール類(6ーニトロベンゾ
イミダゾール)、レゾルシノール類などがあげら
れる。
本発明のハロゲン化銀写真感光材料はその塗布
液に通常用いられる写真用硬膜剤として例えばア
ルデヒド系、アジリジン系、イソオキサゾール
系、エポキシ系、ビニールスルホン系、アクリロ
イル系、カルボジイミド系、マレイミド系、アセ
チレン系、メタンスルホン酸エステル系、トリア
ジン系、高分子型などの硬膜剤が使用できる。
また、増粘剤としてたとえば米国特許第
3767410号、ベルギー国特許第558143号各明細書、
ゼラチン可塑剤としてポリオール類、ラテツクス
類などが用いられてさしつかえない。
さらにマツト剤としては英国特許第1221980号
明細書等に記載のものが使用できる。
本発明に係るハロゲン化銀写真感光材料構成要
素中には塗布助剤として例えばサポニン或いはス
ルホコハク酸型界面活性剤、アニオン性界面活性
剤が使用できる。
本発明に適用されるバインダーとしてはゼラチ
ン、及びゼラチン誘導体としてフエニルカルバミ
ルゼラチン、アシル化ゼラチン、フタル化ゼラチ
ン、或いはアクリル酸スチレン、アクリル酸エス
テル、メタアクリル酸、メタアクリル酸エステル
などのエチレン基をもつた重合可能な単量体をゼ
ラチンにグラフト重合したものなどがあり、更に
コロイド状アルブミン、寒天、アラビアゴム、ア
ルギン酸、或いは加水分解されたセルローズアセ
テートアクリルアミド、イミド化ポリアミド、ポ
リビニルアルコール、加水分解されたポリビニル
アセテート等の水溶性ポリマーがあり、これらの
親水性コロイドは、ハロゲン化銀を含有している
層或いは含有していない例えば保護層、中間層、
フイルター層または他の写真感光材料構成要素中
に用いてよい。
本発明をカラー用感光材料に適用する場合に
は、カプラーとして種々なるものを用いることが
でき、たとえばイエローカプラーとしては開鎖ケ
トメチレン型カプラーを、マゼンタカプラーとし
てはピラゾロン系、ピラゾロトリアゾール系、ピ
ラゾリノベンヅイミダゾール系、イミダゾロン系
などの化合物をあげることができる。
また、シアンカプラーとしてはフエノール系、
ナフトール系などで、さらにカラードマゼンタカ
プラー、カラードシアンカプラー、或いは現像抑
制剤放出型カプラー、現像抑制剤放出型物質、ワ
イスカプラー、コンピーテイングカプラーなどが
使用されてよい。
さらに紫外線吸収剤としてチヌビン類を使用し
てもよく、かつ蛍光増白剤、画像安定剤、酸化防
止剤、潤滑剤、金属イオン封鎖剤、乳化分散剤、
などを使用できる。
本発明のハロゲン化銀感光材料にはハロゲン化
乳剤層以外の層として保護層、中間層、フイルタ
ー層、アンチハレーシヨン層、下引層、イラジエ
ーシヨン防止層、裏引層等の機能補助層を有して
よく、使用される支持体としてはバライタ紙、ポ
リエチレン被覆紙、ポリプロピレン合成紙、ガラ
ス板、セルロースアセテート、セルロースナイト
レート、ポリビニルアセタール、ポリプロピレ
ン、例えばポリエチレンテレフタレートなどのポ
リエステルフイルム、ポリアミドフイルム、ポリ
カーボネートフイルム、スチレンフイルムなどが
あり、これらの支持体はそれぞれハロゲン化銀写
真感光材料の使用目的に応じて適宜選択される。
次に本発明に用いられる現像液は、通常用いら
れる型のもので現像剤としてはハイドロキノン、
N−メチル−p−アミノフエノール、1−フエニ
ル−3−ピラゾリドン、パラフエニレンジアミン
類等の単独または組合せで用いられる。また現像
液にはアルカリ剤として、炭酸ナトリウム、炭酸
カリウム、水酸化ナトリウム、水酸化カリウム、
メタホウ酸ナトリウム、アルカノールアミンな
ど、保恒剤として亜硫酸ナトリウム、亜硫酸カリ
ウム、重亜硫酸ナトリウム、ビロ亜硫酸カリウ
ム、ホルムアルデヒド、亜硫酸水素ナトリウム付
加物など、現像カブリ抑制剤として例えば5−ニ
トロベンゾイミダゾール、5−メチルベンゾトリ
アゾール、8−ニトロベンゾトリアゾール、1−
フエニル−5−メルカプトテトラゾールなどのア
ゾール類を必要に応じて適宜使用できる。
さらに硬膜剤として、ゼラチン及びその他の高
分子物を硬化させるものとして公知なアルデヒド
系化合物を用いることができる。好ましいアルデ
ヒド類としては、ジアアルデヒド化合物で、例え
ばグルタルアルデヒド、マレイツクジアルデヒド
及びそれらの重亜硫酸塩などがあげられる。さら
に現像液には3−6−ジヒドロキシピリダジンの
如き酸化防止剤、ポリアミン類、さらにはポリア
ルキレンオキシド化合物、アルキレングリコール
類、アルコール類としてメチルアルコール、ジメ
チルホルムアミド、セロソルブ、ベンジルアルコ
ールなどの有機溶剤、アスコルビン酸など、必要
に応じて用いられる。
また、キレート剤、PH調整剤、緩衝剤なども使
用できる。現像時間は、現像液種類、処理温度、
使用する感光材料などによつて異なるが、通常は
5分内外またはそれ以上もしくは1分以下5秒位
が適当で、現像処理はバツト式又はローラー移送
方式による迅速自動装置にて処理できる。
更に、本発明のハロゲン化銀写真感光材料は、
例えば白黒ネガ用感光材料の場合、現像→定着→
水洗→乾燥、カラーネガ用感光材料の場合、発色
現像→水洗→漂白→水洗→定着→水洗→安定
等々、その適用する感光材料の種類に応じて、
種々の処理工程をとることができる。
本発明のハロゲン化銀写真感光材料としては
種々の型のハロゲン化銀写真感光材料があげられ
る。たとえば一般用白黒感光材料、X線用感光材
料、カラー用感光材料、印刷用感光材料、複写用
感光材料、拡散転写法感光材料、銀色素漂白法感
光材料、特殊感光材料などの任意のものに対して
本発明を有効に適用できるが白黒感光材料におい
て特に効果が顕著である。
以下に具体例により本発明をさらに詳細に説明
するが本発明の実施態様は、これらに限定される
ものではない。
実施例 1
チオ硫酸ナトリウムと塩化金酸ナトリウムを用
いて化学増感したゼラチン沃臭化銀立方体乳剤
(沃化銀含量2モル%平均粒子径1.2μ)1Kgに4
−ヒドロキシ−6−メチル−1,3,3a,7−
テトラザインデンの1%水溶液10ml、サポニンの
10%水溶液30ml、ホルマリンの3%水溶液3mlを
加えた。(なお、この乳剤はハロゲン化銀1モル
当り80gのゼラチンを含む。)
この乳剤を分割して下記の表1に示す化合物を
加え、塗布銀量が7g/m2となるように、保護層
とともにポリエチレンテレフタレート青着色支持
体に塗布して試料を作製した。
これらの試料をJIS法に基きKS−1型センシト
メーター(小西六写真工業株式会社製)により白
色露光を与えたのちタンク現像を行ない、乾燥後
濃度を測定し通常のセンシトメトリー法に従い、
カブリ(F)、比感度(RS)、コントラスト
(γ)、最高濃度(Dmax)を測定した。
用いた現像液は下記組成()で処理条件は、
20℃4分30秒である。
現像液()組成
亜硫酸ソーダ 70g
ハイドロキノン 10g
炭酸ソーダ1水塩 30g
1−フエニル−3−ピラゾリドン 0.35g
ブロムカリ 4g
水で1にする。
結果を表1に示す。Examples include [Formula] groups. Examples of the fluoroalkylene group include -CF2
A CF2- group may be mentioned. Specific examples of the compounds related to the present invention are listed below, but the present invention is of course not limited to these uses. The compound according to the invention can be contained in the emulsion layer, other layers adjacent to the emulsion layer (for example, a protective layer), or both. The amount added is preferably 10 mg to 1 g, more preferably 20 mg to 300 mg, per mole of silver halide used in the silver halide photographic material of the present invention. It may be added at any time during or before coating the silver halide emulsion, but if the layer to be contained is an emulsion layer, it is preferably added after chemical ripening or during coating. Various silver halides can be used in the silver halide emulsion layer according to the present invention. Examples include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Crystal form of silver halide grains,
There are no limitations on the crystal structure, grain size, grain size distribution, etc. For example, the crystal shape may be cubic, octahedral, or tetradecahedral, normal crystal, or twin crystal. Further, it may be an emulsion with a wide particle distribution or a monodisperse emulsion. The crystal structure may be uniform, the inside and outside may have different compositions, it may have a layered structure, or silver halides of different compositions may be joined by epitaxial bonding. good. Further, the latent image may be formed mainly on the surface or inside. The silver halide emulsion can be sensitized using conventional chemical sensitization, that is, sulfur sensitization using sodium thiosulfate, allylthiocarbamide, thiourea, allyl thiocyanate, etc., and noble metal sensitization using platinum chloride. Potassium acid, ammonium palladate chloride or salts of noble metals such as ruthenium, rhodium, iridium, platinium, etc. can also be used. Sensitization can also be achieved by using these noble metal salts in combination with a sulfur sensitizer, and further with rhodanammonium as an auxiliary agent. Furthermore, selenium sensitization methods include methods using selenourea, N-N dimethylselenourea, N-dimethylselenourea, etc., and reduction sensitization methods include methods using tin salts, methods using polyamines, and quaternary ammonium salts. Sensitization can also be achieved depending on the method used. Furthermore, sensitization methods using polyalkylene oxide compounds and sensitization methods using thioethers can also be used. The silver halide emulsion according to the present invention can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye. Various sensitizing dyes can be used, and one or two sensitizing dyes may be used.
More than one species can be used in combination. Dyes that can be advantageously used in the present invention include methine dyes and styryl dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, oxonol, and hemioxonol. In particular, US Pat.
Specifications of each issue, Special Publication No. 43-13821, No. 44-32753
No. 46-18106, No. 47-8741, No. 47-37443
The sensitizing dyes described in each publication and JP-A-48-89722 are effective in the present invention. The main specific pigment is 3,3'-di-
(3-sulfopropyl)selenacarbocyanine hydroxide, 5,5'-diphenyl-3,3'-di-
(3-Sulfopropyl)oxacyanine hydroxide, 5,5'-diphenyl-3,3'-di-(3-
sulfopropyl)oxacarbocyanine hydroxide, 3-allyl-5-[1-methyl-2(1H)
Piperidylidene] rhodanine, 3-(4-sulfobutyl)-1'-ethyl-5'-methylselenium-2'-cyanine hydroxide, 1-hydroxyethyl-3
-phenyl-5-[3(3-sulfopropyl)-2
-Benzoxazolinidene]ethylidene-2-thiohydantoin sodium salt, 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide, 5,
5'-diphenyl-9-ethyl-3,3'-di(3-
sulfopropyl)oxacarbocyanine hydroxide, 5,5',6,6'-tetrachloro-1,1'-
Diethyl-3,3'-di-(4-sulfobutyl)benzimidazolocarbocyanine hydroxide sodium salt, 5,5'-di-(butoxycarbonyl)-
1,1'-diethyl-3,3'-di-(3-sulfopropyl)benzimidazolocarbocyanine hydroxide, 5,5'-dichloro-1,3'-diethyl-
6'-methyl-3-(4-sulfobutyl)benzimidazoloxacarbocyanine hydroxide,
5,5'-dichloro-9-ethyl-3,3'-(dicarboxyethyl)-thiacarbocyanine hydroxide, 5,5'-dichloro-3,9-diethyl-
3'-(3-sulfopropyl)-thiacarbocyanine hydroxide, 5,5'-dimethyl-9-ethyl-
3,3'-di-(3-sulfopropyl)thiacardi(3-sulfopropyl)4,5,4',5'-dibenzothiacarbocyanine hydroxide, 9-ethyl-3,3'-di(3- sulfopropyl)-5,6,
Examples include 5',6'-dibenzoxacarbocyanine hydroxide. The silver halide emulsion according to the present invention is used as a stabilizer and a fog suppressant, for example, in the specifications of US Pat. No. 2,444,607, US Pat. No. 2,716,062, US Pat. No. 2058626,
Specifications of No. 211841, Special Publication No. 43-4133, No. 39
-2825 publications, JP-A-50-22626, JP-A-50-
You may apply the method described in each publication such as No. 25218,
Particularly preferred compounds include 4-hydroxy-
6-methyl-1,3,3a,7-tetrazaindene, 4-hydroxy-cyclopentano[f]-1,
3,3a,7-tetrazaindene or gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercabutanes (1-phenyl-5-mercabutotetrazole, 2-mercabutane) Examples include benzothiazole) benzotriazoles (5-brombenzotriazole, 4-methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole), and resorcinols. The silver halide photographic material of the present invention has photographic hardeners commonly used in its coating solution, such as aldehyde-based, aziridine-based, isoxazole-based, epoxy-based, vinyl sulfone-based, acryloyl-based, carbodiimide-based, maleimide-based, Hardening agents such as acetylene type, methanesulfonic acid ester type, triazine type, and polymer type can be used. In addition, as a thickening agent, for example, U.S. Pat.
3767410, Belgian Patent No. 558143,
Polyols, latexes, etc. may be used as gelatin plasticizers. Further, as a matting agent, those described in British Patent No. 1221980 and the like can be used. In the components of the silver halide photographic light-sensitive material according to the present invention, for example, saponin or sulfosuccinic acid type surfactants, and anionic surfactants can be used as coating aids. The binder applicable to the present invention includes gelatin, and gelatin derivatives such as phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin, or ethylene groups such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester. There are gelatin graft-polymerized polymerizable monomers with These hydrophilic colloids can be used in layers with or without silver halide, such as protective layers, intermediate layers, etc.
It may be used in filter layers or other photographic material components. When the present invention is applied to color photosensitive materials, various couplers can be used. For example, an open-chain ketomethylene coupler can be used as a yellow coupler, and a pyrazolone type, pyrazolotriazole type, or pyrazolone type coupler can be used as a magenta coupler. Examples include compounds such as nobenzimidazole and imidazolone. In addition, cyan couplers include phenolic,
In addition to the naphthol type, colored magenta couplers, colored cyan couplers, development inhibitor-releasing couplers, development inhibitor-releasing substances, Weis couplers, competing couplers, etc. may be used. Furthermore, tinuvins may be used as ultraviolet absorbers, and optical brighteners, image stabilizers, antioxidants, lubricants, sequestering agents, emulsifying dispersants,
etc. can be used. The silver halide photosensitive material of the present invention has functional auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a subbing layer, an irradiation prevention layer, and a backing layer as layers other than the halogenated emulsion layer. Supports that can be used include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polyamide films, and polycarbonate films. , styrene film, etc., and these supports are appropriately selected depending on the intended use of the silver halide photographic material. Next, the developer used in the present invention is of a commonly used type, and the developer includes hydroquinone,
N-methyl-p-aminophenol, 1-phenyl-3-pyrazolidone, paraphenylenediamines, etc. are used alone or in combination. The developer also contains alkaline agents such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide,
Preservatives such as sodium metaborate and alkanolamine; preservatives such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium birosulfite, formaldehyde, and sodium bisulfite adduct; development fog inhibitors such as 5-nitrobenzimidazole and 5-methyl; Benzotriazole, 8-nitrobenzotriazole, 1-
Azoles such as phenyl-5-mercaptotetrazole can be used as appropriate. Further, as a hardening agent, an aldehyde compound known for hardening gelatin and other polymers can be used. Preferred aldehydes include dialdehyde compounds such as glutaraldehyde, maleic dialdehyde, and bisulfites thereof. Furthermore, the developer contains antioxidants such as 3-6-dihydroxypyridazine, polyamines, polyalkylene oxide compounds, alkylene glycols, organic solvents such as methyl alcohol, dimethylformamide, cellosolve, benzyl alcohol, and ascorbin. Acids etc. are used as necessary. Additionally, chelating agents, PH adjusting agents, buffering agents, etc. can also be used. The development time depends on the type of developer, processing temperature,
Although it varies depending on the photosensitive material used, the appropriate time is usually about 5 minutes or longer, or less than 1 minute and 5 seconds, and the development process can be carried out using a rapid automatic device using a vat type or a roller transfer type. Furthermore, the silver halide photographic material of the present invention includes:
For example, in the case of black and white negative photosensitive materials, development → fixing →
Water washing→drying, in the case of color negative photosensitive materials, color development→water washing→bleaching→water washing→fixing→water washing→stabilization, etc., depending on the type of photosensitive material to which it is applied.
Various processing steps can be taken. The silver halide photographic material of the present invention includes various types of silver halide photographic materials. For example, any material such as general black and white photosensitive materials, X-ray photosensitive materials, color photosensitive materials, printing photosensitive materials, copying photosensitive materials, diffusion transfer method photosensitive materials, silver dye bleaching method photosensitive materials, special photosensitive materials, etc. Although the present invention can be effectively applied to black and white photosensitive materials, the effect is particularly remarkable. The present invention will be explained in more detail below using specific examples, but the embodiments of the present invention are not limited to these. Example 1 Gelatin silver iodobromide cubic emulsion chemically sensitized using sodium thiosulfate and sodium chloroaurate (silver iodide content 2 mol% average grain size 1.2μ) 4 to 1 kg
-Hydroxy-6-methyl-1,3,3a,7-
10ml of 1% aqueous solution of tetrazaindene, saponin
30 ml of a 10% aqueous solution and 3 ml of a 3% aqueous formalin solution were added. (This emulsion contains 80 g of gelatin per mole of silver halide.) This emulsion is divided into parts, the compounds shown in Table 1 below are added, and a protective layer is coated so that the amount of silver coated is 7 g/ m2 . A sample was prepared by coating the same material on a polyethylene terephthalate blue colored support. These samples were exposed to white light using a KS-1 type sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.) based on the JIS method, then developed in a tank, and after drying, the density was measured and the density was measured according to the usual sensitometric method.
Fog (F), specific sensitivity (RS), contrast (γ), and maximum density (Dmax) were measured. The developer used had the following composition () and the processing conditions were as follows:
20℃ for 4 minutes and 30 seconds. Composition of developer () Sodium sulfite 70g Hydroquinone 10g Sodium carbonate monohydrate 30g 1-phenyl-3-pyrazolidone 0.35g Brompotash 4g Make 1 with water. The results are shown in Table 1.
【表】【table】
【表】
添加量はハロゲン化銀1モル当たりの量であ
り、RSは本発明に関る化合物を添加しない試料
を基準の100とした。
またγは写真業界で一般的に用いる乳剤特性曲
線上の濃度1.0と2.0の間の直線部分の傾きの横軸
となす角θのtanθで表わしたものである。
これらの結果から明らかなように、本発明に関
る化合物を添加することによつてカブリの上昇を
伴なうことなく感度が上昇し、かつ、コントラス
ト、最高濃度が向上する。
実施例 2
実施例1と同様にして調製した乳剤と、通常の
塗布助剤、を加えて調製した保護層用ゼラチン溶
液とを用いて、本発明に関る化合物及び下記に示
す本発明以外の化合物(A),(B),(C)をそれぞれ乳剤
層あるいは保護層に添加して試料を作製した。塗
布量については、乳剤層は銀にして7g/m2、保
護層はゼラチンにして1.5g/m2とした。塗布し
た試料を、温度23℃相対温度55%の条件の下に放
置し、1日後、15日後、60日後に、実施例1と同
様の方法で露光した後、現像液()で現像処理
を行ない、乳剤特性を測定した。結果を表2に示
す。
写真特性の記号は実施例1と同義である。
[Table] The amount added is the amount per mole of silver halide, and RS is 100 based on the sample to which no compound related to the present invention is added. Further, γ is expressed as tanθ, which is the angle θ formed with the horizontal axis of the slope of the straight line portion between densities 1.0 and 2.0 on the emulsion characteristic curve generally used in the photographic industry. As is clear from these results, by adding the compound according to the present invention, sensitivity is increased without increasing fog, and contrast and maximum density are also improved. Example 2 Using an emulsion prepared in the same manner as in Example 1 and a gelatin solution for a protective layer prepared by adding a usual coating aid, compounds related to the present invention and compounds other than the present invention shown below were prepared. Samples were prepared by adding compounds (A), (B), and (C) to the emulsion layer or protective layer, respectively. The coating amount was 7 g/m 2 in terms of silver for the emulsion layer and 1.5 g/m 2 in terms of gelatin for the protective layer. The coated sample was left under conditions of a temperature of 23°C and a relative temperature of 55%, and after 1 day, 15 days, and 60 days, it was exposed in the same manner as in Example 1, and then developed with a developer (). The emulsion properties were measured. The results are shown in Table 2. Symbols for photographic characteristics have the same meanings as in Example 1.
【表】【table】
【表】
本発明に用いる化合物を添加した試料は化合物
(A),(B)あるいは化合物(C)を添加した試料と比べ、
コントラスト、最高濃度の向上に優れた効果を有
するとともに、経時による変化も著しく少ないこ
とがわかる。また本発明に用いる化合物は乳剤層
だけでなく、保護層に添加した場合も同様の効果
をもたらすことがわかる。[Table] Samples to which the compound used in the present invention was added are compounds
Compared to samples containing (A), (B) or compound (C),
It can be seen that it has an excellent effect on improving contrast and maximum density, and also shows very little change over time. Furthermore, it can be seen that the compound used in the present invention produces similar effects when added not only to the emulsion layer but also to the protective layer.
Claims (1)
とも1種を含有することを特徴とするハロゲン化
銀写真感光材料。 一般式() (式中、R1,R3,R4及びR6は炭素数1〜5ま
での低級アルキル基を表し、R2及びR5は炭素数
1〜15までのアルキル基、アリール基、アラルキ
ル基、ヒドロキシアルキル基またはヘテロ環基を
表す。 A,A′及びBはアルキレン基、アリーレン基、
アラルキレン基又はフルオロアルキレン基を表
し、これらは同じであつても異つていてもよい。)[Scope of Claims] 1. A silver halide photographic material containing at least one compound represented by the following general formula (). General formula () (In the formula, R 1 , R 3 , R 4 and R 6 represent lower alkyl groups having 1 to 5 carbon atoms, and R 2 and R 5 represent alkyl groups, aryl groups, and aralkyl groups having 1 to 15 carbon atoms. , represents a hydroxyalkyl group or a heterocyclic group. A, A' and B are an alkylene group, an arylene group,
It represents an aralkylene group or a fluoroalkylene group, and these may be the same or different. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9152582A JPS58208741A (en) | 1982-05-28 | 1982-05-28 | Silver halide photosensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9152582A JPS58208741A (en) | 1982-05-28 | 1982-05-28 | Silver halide photosensitive material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58208741A JPS58208741A (en) | 1983-12-05 |
JPH0454934B2 true JPH0454934B2 (en) | 1992-09-01 |
Family
ID=14028835
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9152582A Granted JPS58208741A (en) | 1982-05-28 | 1982-05-28 | Silver halide photosensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58208741A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62269137A (en) * | 1986-05-16 | 1987-11-21 | Konika Corp | Silver halide photographic sensitive material appropriate for x-ray photography |
JPH0711683B2 (en) * | 1987-11-05 | 1995-02-08 | 富士写真フイルム株式会社 | Silver halide photographic emulsion |
-
1982
- 1982-05-28 JP JP9152582A patent/JPS58208741A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS58208741A (en) | 1983-12-05 |
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